CN105493203B - Transparency electrode and its manufacture method - Google Patents
Transparency electrode and its manufacture method Download PDFInfo
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- CN105493203B CN105493203B CN201480046100.6A CN201480046100A CN105493203B CN 105493203 B CN105493203 B CN 105493203B CN 201480046100 A CN201480046100 A CN 201480046100A CN 105493203 B CN105493203 B CN 105493203B
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1283—After-treatment of the printed patterns, e.g. sintering or curing methods
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0108—Transparent
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/026—Nanotubes or nanowires
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
- H05K3/106—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam by photographic methods
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Abstract
The problem of the present invention is to provide a kind of transparency electrode and its manufacture method, and transparency electrode uses metal nanometer line and/or metal nano-tube to have both surface smoothness, electric conductivity and translucency, and productivity is high as conductive compositions.Solution is, thermosetting or thermoplastic adhesive resin of the scope without mobility made at 5~40 DEG C is dissolved in solvent and obtains solution, metal nanometer line and/or metal nano-tube is set to be scattered in the solution, obtain the transparent conductivity ink for containing the mass parts of described adhesive resin 100~2500 relative to the metal nanometer line and/or the mass parts of metal nano-tube 100, the electrode pattern of desired shape is printed on substrate using the transparent conductivity ink, to printed electrode pattern irradiating pulsed light, thus it is 0.1~500 Ω/ to obtain sheet resistance, arithmetic average roughness Ra≤the 5nm on surface transparency electrode.
Description
Technical field
The present invention relates to transparency electrode and its manufacture method.
Background technology
The tablet terminals such as the display equipment of organic EL (electroluminescent) display, liquid crystal display etc, smart mobile phone
Or in touch panel, solar cell etc. used in various input units etc., the transparency electrode that can pass through light is necessary structure
Into part.
Nesa coating used in these transparency electrodes uses ITO (tin indium oxide) at present.But for ITO indium
For rare metal, therefore, the stabilisation of supply and price turns into problem in recent years.Further, since ITO film forming uses sputtering method
And vapour deposition method etc., so vacuum manufacture device is needed, and not only manufacturing time is grown, and also cost is also high.In addition, ITO is because of bending
Easily crack and destroy etc. physical stress, so being difficult to assigning flexible substrate application.Therefore, carried out solving this
The ITO of a little problem points replaces the exploration of material.
Therefore, in " ITO replaces material ", as need not use vacuum manufacture device can coating film forming material, example
As report has (i) poly- (3,4- ethyldioxythiophenes)/poly- (4- styrene sulfonic acids) (PEDOT:PSS) (referring for example to patent text
Offer 1) etc. the conductive material of macromolecular conductive material and (ii) containing metal nanometer line (referring for example to the He of patent document 2
Non-patent literature 1) and the conductive material (referring for example to patent document 3) of (iii) containing CNT etc. contain nanometer
The conductive material of structural conductive composition.
Among them, it was recently reported that the conductive material containing metal nanometer line of (ii) shows low sheet resistance and height
Light transmittance (referring for example to patent document 2 and non-patent literature 1), and due to also having flexibility, therefore be suitable as
" ITO replaces material ".
Here, for example in the case of organic EL element, in order to form the ultrathin membrane of organic compound on electrode, if
Using the low transparency electrode of surface smoothness, then it can cause the function of organic EL element to reduce.Therefore, excellent is required to transparency electrode
Different surface smoothness.
In the case where forming transparency electrode by the above-mentioned conductive material containing metal nanometer line, to improve transparency electrode
Surface smoothness, it is proposed that form conductive layer on the high support of flatness using metal nanometer line, and be transferred to other
The method (patent document 4) of support.But cementability, the fissility of the bonding agent and support or conductive layer for transfer
Balanced adjustment it is difficult, it is difficult to completely transferred.Additionally, there are the coating of bond layer, solidification, support are mutual
The problem of processes such as fitting, stripping are more, and cost is high.
In addition, there is the method that transparency electrode is manufactured by following process disclosed in patent document 5：Metal is contained by coating
The liquid of nano wire and adhesive and form the process of the first conductive layer, process that above-mentioned adhesive is crosslinked or solidified, will contain
Conductive macromolecule and non-conductive high molecular aqueous dispersion are coated on the first conductive layer and form the second conductive layer
Process and pattern printing metal nanometer line remove liquid and go forward side by side the process that water-filling is washed.But to ensure that surface smoothness is formed
2 Rotating fields, therefore, manufacturing process increases, unfavorable on this point in productivity.
Prior art literature
Patent document
Patent document 1：No. 4077675 publication of (Japan) patent
Patent document 2：(Japanese) Patent Laid-Publication 2009-505358 publications
Patent document 3：(Japan) JP 2003-100147 publications
Patent document 4：WO2010/106899 publications
Patent document 5：(Japan) JP 2010-205532 publications
Non-patent literature
Non-patent literature 1:Shih-Hsiang Lai,Chun-Yao Ou,Chia-Hao Tsai,Bor-Chuan
Chuang,Ming-Ying Ma,and Shuo-Wei Liang；SID Symposium Digest of Technical
Papers,Vol.39,Issue 1,pp.1200-1202(2008)
The content of the invention
Invent problem to be solved
It is an object of the present invention to provide a kind of transparency electrode and its manufacture method, transparency electrode uses metal nanometer line
And/or metal nano-tube has both surface smoothness, electric conductivity and translucency, and productivity is high as conductive compositions.
For solving the technical scheme of problem
To achieve the above object, an embodiment of the present invention provides a kind of transparency electrode, it is characterised in that is received containing metal
Rice noodles and/or metal nano-tube and 5~40 DEG C scope without mobility thermosetting or thermoplastic adhesive tree
Fat, the sheet resistance of the electrode are 0.1~500 Ω/, arithmetic average roughness Ra≤5nm of the electrode surface, described
Electrode is made up of single conductive layer.
It is preferred that the arithmetic average roughness Ra≤4nm on the surface.
It is preferred that the content of the metal nanometer line and/or metal nano-tube in the transparency electrode is 4~50 mass %.
It is preferred that the metal of the metal nanometer line and/or metal nano-tube contains silver.
It is preferred that described adhesive resin is selected from poly N-vinyl pyrrolidone, poly-N-vinylcaprolactam, poly- N- second
At least one of alkenyl acetamide, polyvinylformamide.
In addition, another embodiment of the present invention provides a kind of manufacture method of transparency electrode, it is characterised in that has following
Process：
The process of the electrode pattern of shape, the transparent conductivity desired by being printed using transparent conductivity ink on substrate
Ink obtains as follows：It is dissolved in thermosetting or thermoplastic binder resins of the scope without mobility at 5~40 DEG C
Solvent and obtain solution, metal nanometer line and/or metal nano-tube is scattered in the solution, the transparent conductivity ink
In, relative to the metal nanometer line and/or the mass parts of metal nano-tube 100, the bonding containing 100~2500 mass parts
Agent resin；And
To the process of the electrode pattern irradiating pulsed light of printing.
Formed in addition, another embodiment of the present invention provides a kind of transparency electrode with transparent conductivity ink, it is characterised in that
Containing metal nanometer line and/or metal nano-tube, solvent, be dissolved in solvent in 5~40 DEG C of scope without mobility
Thermosetting or thermoplastic insulating properties adhesive resin, relative to the metal nanometer line and/or the mass of metal nano-tube 100
Part, contain the mass parts of described adhesive resin 100~2500.
Invention effect
According to the present invention it is possible to obtain using metal nanometer line and/or metal nano-tube as conduction using high productivity
Composition, and have both the transparency electrode of surface smoothness, electric conductivity and translucency.
Brief description of the drawings
Fig. 1 is the figure for illustrating the definition of pulsed light.
Fig. 2 is the figure of the SEM pictures of nano silver wire for representing to make in embodiment.
Embodiment
Hereinafter, the mode (hereinafter referred to as embodiment) for implementing the present invention is illustrated with reference to the accompanying drawings.
The transparency electrode of embodiment, using containing 5~40 DEG C scope do not have mobility thermosetting or thermoplastic
Property adhesive resin solution (decentralized medium) in be dispersed with the transparent conductivity ink of metal nanometer line and/or metal nano-tube
The electrode pattern of shape desired by printing on substrate, by the pattern irradiating pulsed light after printing, assigning electric conductivity.
This, 5~40 DEG C of room temperatures for referring to generally be printed.
As above-mentioned thermosetting or thermoplastic adhesive resin of the scope without mobility at 5~40 DEG C, as long as
It is transparent resin, its own no mobility and is dissolvable in water in solvent at room temperature, it is possible to is made without particular limitation
With, but more preferably heat resistance is high and hygroscopicity is low.Here, thermosetting resin refers to be dissolvable in water solvent in the uncured state
In thermosetting resin.Thermosetting resin is preferably by light irradiation described later and heat cure.As these adhesive resins, such as
Can enumerate acrylic resin, epoxy resin, Epocryl, chlorinated polyethylene, unsaturated polyester resin,
Allyl ester resin, dially phthalate (DAP) resin, polyurethane resin, silicone resin, polyester resin, makrolon
It is resin, polyamide (nylon), amorphous polyolefin resin, polystyrene, polyvinyl acetate, poly N-vinyl acid amides, poly-
4-methyl-1-pentene etc..Wherein, the poly N-vinyl pyrrolidone excellent with the compatibility of silver, poly- N- second can particularly be enumerated
The poly N-vinyl acid amides such as alkenyl caprolactam, poly N-ethylene yl acetamide, polyvinylformamide or the transparency are excellent
Cyclic olefin polymer (COP), cyclic olefine copolymer (COC), epoxy resin, chlorinated polyethylene, polyurethane resin etc. are exhausted
Edge resin, but known electroconductive resin can also be used as needed.
Particularly, poly N-vinyl pyrrolidone, poly-N-vinylcaprolactam, poly N-ethylene yl acetamide, poly- N- second
The poly N-vinyl such as alkenyl formamide amide-type can also use when synthesizing nano wire, furthermore it is possible to be used as in post synthesis
Have both the Protective coatings of anti-aggegation and add, so by the fabrication stage superfluous use in nano wire, not only manufacture and also hold
Easily, and the quality of electrode can also improve, it is advantageous to.
In addition, above-mentioned metal nanometer line and metal nano-tube are the metals of the diameter with nano-grade size, metal nano
Line is the conductive material for having wire shape, and metal nano-tube is the porous or non-porous electric conductivity material with tubular form
Material.In this specification, " wire " and " tubulose " is wire, but the former refers to center not to be hollow, during the latter refers to that center is
It is empty.Character can be it is soft can also be upright and outspoken.Metal nanometer line or metal nano-tube can use either of which,
Both can be used in mixed way.
As the species of metal, can enumerate in gold, silver, platinum, copper, nickel, iron, cobalt, zinc, ruthenium, rhodium, palladium, cadmium, osmium, iridium
At least one and by these metallic combinations alloy etc..In order to obtain having low sheet resistance and the transmission of high full light
The film of rate, preferably comprise at least one of gold, silver and copper.These metals are because electric conductivity is high, so obtaining certain table
During surface resistance, metal density shared in face can be reduced, it is thereby achieved that high full light transmittance.
In these metals, further preferably golden or silver at least one.As optimal mode, silver-colored nanometer can be enumerated
Line.
The fineness degree of diameter of metal nanometer line and/or metal nano-tube in transparent conductivity ink, the length of major axis and
Aspect ratio preferably has certain distribution.The distribution is selected, so that the film obtained by the transparent conductivity ink of present embodiment
As the film that full light transmittance is high and sheet resistance is low.Specifically, the diameter of metal nanometer line and metal nano-tube
Fineness degree is averagely preferably 1~500nm, more preferably 5~200nm, more preferably 5~100nm, particularly preferably 10
~70nm.In addition, the length of the major axis of metal nanometer line and/or metal nano-tube is averagely preferably 1~100 μm, more preferably
For 1~80 μm, more preferably 5~80 μm, particularly preferably 10~50 μm.For metal nanometer line and/or metal nano
Pipe, average and major axis being averaged for length of the fineness degree of diameter meet above range, and the average of aspect ratio is preferably big
In 5, more preferably more than 10, more preferably more than 100, particularly preferably more than 200.Here, aspect ratio is by gold
The average fineness degree of the diameter of category nano wire and/or metal nano-tube is designated as b, the average length of major axis is designated as to a feelings
Under condition, the value obtained by a/b.A and b can use SEM (SEM) to determine.
As the manufacture method of metal nanometer line and/or metal nano-tube, known manufacture method can be used.For example,
Nano silver wire can by using polyalcohol (Poly-ol) method, in the presence of PVP by silver nitrate reduction and
Synthesis (with reference to Chem.Mater., 2002,14,4736).Nanowires of gold similarly can be by PVP
In the presence of gold chloride hydrate is reduced and synthesized (with reference to J.Am.Chem.Soc., 2007,129,1733).On nano silver wire
And extensive synthesis and the refined technology of nanowires of gold, in International Publication WO2008/073143 pamphlets and International Publication
There is detailed description in No. 2008/046058 pamphlet.Gold nanotubes with loose structure can by using nano silver wire as
Model, chlorauric acid solution is reduced and synthesized.Here, the nano silver wire as model passes through the redox reaction with gold chloride
And dissolution is into solution, its result formed with loose structure gold nanotubes (with reference to J.Am.Chem.Soc., 2004,126,
3892-3901)。
The transparency electrode formation transparent conductivity ink of embodiments of the present invention can be by making the above-mentioned model at 5~40 DEG C
Enclose (room temperature) thermosetting or thermoplastic adhesive resin without mobility to be dissolved in solvent, and make metal nanometer line
And/or metal nano-tube is dispersed therein to prepare.As solvent as used herein, as long as be generally used for intaglio printing,
The solvent of silk-screen printing, intaglio offset, flexographic printing etc., it is possible to use without particular limitation.In the situation of intaglio printing
Under, using the relatively low solvent of boiling point, in the case of silk-screen printing, use the higher solvent of boiling point.
The solvent relatively low as the boiling point available for intaglio printing, boiling point are preferably less than more than 50 DEG C 200 DEG C, more preferably
For less than 150 DEG C, such as using ketone system, ethyl acetate, acetic acid such as the aromatic series such as toluene, dimethylbenzene hydrocarbon system, acetone, butanone just
The organic solvents such as the alcohol series solvents such as the ester such as propyl ester system, isopropanol, normal propyl alcohol, 2- butanol, isobutanol, n-butanol.
The solvent higher as the boiling point available for silk-screen printing, boiling point is preferably less than 360 DEG C more than 120 DEG C, more excellent
Elect more than 150 DEG C as, specifically, acetate of butyl carbitol, butyl carbitol, terpineol, isobornyl hexamethylene can be enumerated
Alcohol (trade name：テ Le ソ Le Block MTPH, Japanese テ Le ペ Application systems), dimethylbenzene, double Ethoxyethanes, ethylene glycol, propane diols etc..
In addition, these solvents can use a kind or combine two or more use.
It is good from its as the content of metal nanometer line and/or metal nano-tube in the transparent conductivity ink of present embodiment
Good patternability, high electric conductivity and the good light of good dispersiveness and the film obtained by transparent conductivity ink
From the viewpoint of learning characteristic, relative to transparent conductivity ink gross mass, metal nanometer line and/or metal nano-tube are 0.01~10
The amount of quality % amount, more preferably 0.05~2 mass %.If metal nanometer line and/or metal nano-tube are less than 0.01 matter
% is measured, then for the electric conductivity desired by ensuring, it is necessary to print transparent conductive film layer very thickly, the difficulty not only printed carries
Height, and it is difficult to maintenance pattern when drying.In addition, if more than 10 mass %, then to ensure desired transparency, it is necessary to
Very unfertile land prints, and is in this case also difficult to print.
In addition, as in the heat for not having mobility at room temperature to the metal nanometer line and/or metal nano-tube application
The use level of solidity or thermoplastic adhesive resin, according to used resin, best fit amount is also different, but generally
Relative to metal nanometer line and/or the mass parts of metal nano-tube 100, the amount of the mass parts of preferably 100 mass parts~2500 is more excellent
Elect the amount of the mass parts of 150 mass parts~2000 as.If adhesive resin is below 100 mass parts, there is surface smoothness drop
Low trend.In addition, if more than 2500 mass parts, then become to be difficult to reduce sheet resistance by irradiating pulsed light.
The transparent conductivity ink of present embodiment can also contain mentioned component (gold in the range of its property is not damaged
Belong to nano wire, metal nano-tube, adhesive resin) beyond any condition, for example improve and the moistening of the wetability of base material point
Powder, surface conditioner, defoamer, thixotropic agent, levelling agent, preservative, closely sealed accelerator, surfactant etc..
As Ricinate, DISPERBYK (registration mark) -106, DISPERBYK (registration mark) -108 can be enumerated
(PVC ッ Network ケ ミ ー ジ ャ パ Application (strain) system), as surface conditioner, BYK (registration mark) -300, BYK (registrations can be enumerated
Trade mark) -306 (PVC ッ Network ケ ミ ー ジ ャ パ Application (strain) systems), as defoamer, BYK (registration mark) -051, BYK can be enumerated
(registration mark) -054 (PVC ッ Network ケ ミ ー ジ ャ パ Application (strain) system), as thixotropic agent, can enumerate BYK (registration mark) -
405th, BYK (registration mark) -410 (PVC ッ Network ケ ミ ー ジ ャ パ Application (strain) system), as levelling agent, BYKETOL (notes can be enumerated
Volume trade mark)-OK (PVC ッ Network ケ ミ ー ジ ャ パ Application (strain) system), as preservative, BTA etc. can be enumerated, as closely sealed rush
Enter agent, 2- hydroxymethyl fibre elements etc. can be enumerated, as surfactant, trade name F-472SF (DIC (strain) systems) etc. can be enumerated.
The transparent conductivity ink of present embodiment can be by the way that by mentioned component, in a known manner and suitably selection is stirred
Mix, mix, heating, cooling down, dissolving, disperseing etc. and manufacturing.
The preferable viscosity of the transparent conductivity ink of present embodiment is different according to printing process, but in intaglio printing
In the case of, the viscosity at 25 DEG C is preferably 50~10000mPas, more preferably 300~5000mPas.In silk-screen printing
In the case of, the viscosity at 25 DEG C is preferably 100~2 × 105MPas, more preferably 1 × 103~5 × 104mPa·s.In addition,
Viscosity is the value determined using cone-plate type rotation viscometer (cone-plate type).In embodiment described later, comparative example, Block Le is used
((height is viscous by template formula CP-40 (being 26~87200mPas during low viscosity) or CP-52 by ッ Network Off ィ ー ルド society HBDV-II+Pro
It is 800~2620000mPas when spending)).
Using the transparent conductivity ink being prepared, pass through intaglio printing, silk-screen printing, ink jet printing, flexographic printing etc.
Carry out the pattern printing of the desired shape of transparency electrode.
As the substrate for carrying out pattern printing, hardness is not particularly limited.Can use has rigid substrate, can also
Use the substrate with flexibility.In addition, though can also colour, but it is preferably transparent the higher the better under visible ray.As base
Plate, such as glass, polyimides, makrolon, polyether sulfone, acrylic resin, polyester (poly terephthalic acid second two can be enumerated
Alcohol ester, PEN etc.), polyolefin, the material such as polyvinyl chloride.It is preferred that they have high light transmittance and
Low haze value.On substrate, the circuit of TFT elements etc. can be further formed, the feature material such as colour filter can also be formed
Material.Alternatively, it is also possible to be laminated multiple substrates.
Coating weight as from transparent conductivity ink to base material, consider to be determined according to the thickness of the transparency electrode required by purposes
It is fixed.The thickness of transparency electrode can be adjusted by adjusting the coating weight of transparent conductivity ink and the condition of coating method.
The transparent conductivity ink of (coating) is printed, coating material is heated as needed and makes its drying.Heating-up temperature
Different according to the liquid-like constituents for forming decentralized medium, but if drying temperature is too high, then the pattern formed sometimes can not be kept.
Therefore, drying temperature is up to less than 120 DEG C, more preferably less than 100 DEG C.Particularly initial drying temperature is critically important, because
This is particularly preferred：The drying since 40~80 DEG C or so, and as needed periodically in the scope heating no more than 120 DEG C.
Sheet resistance, full light transmittance and haze value for transparency electrode, can be by adjusting its thickness, i.e., by suitable
Composition, coating weight and coating method etc. of transparent conductivity ink used in preferably selecting is set to desired value.
Generally, thickness is thicker, then sheet resistance and full light transmittance become lower.In addition, in transparent conductivity ink
The concentration of metal nanometer line or metal nano-tube is higher, and sheet resistance and full light transmittance become lower, and mist degree also uprises.
The transparent conductivity ink of present embodiment, although the sheet resistance also having in certain degree, which is only dried, to be reduced,
More efficiently to reduce and irradiating pulsed light.
In this specification, (irradiation time) is the light of short time during " pulsed light " refers to light irradiation, is repeatedly being entered repeatedly
In the case of row light irradiation, as shown in figure 1, referring to have during the first light irradiation during (on) and the second light irradiation between (on)
There is the light irradiation at (irradiation interval (off)) during not irradiation light.The luminous intensity that pulsed light is represented in Fig. 1 is constant, but 1
During secondary light irradiation in (on), luminous intensity can also change.Above-mentioned pulsed light is from the light for possessing the flash lamps such as xenon flash lamp
Source is irradiated.Using such light source, to the metal nanometer line or metal nano-tube irradiating pulsed light being piled up on aforesaid substrate.Instead
In the case that note in reply is penetrated n times, 1 circulation (on+off) in Fig. 1 is repeated n times.In addition, in the case where irradiating repeatedly,
When carrying out next pulse light irradiation, in order to prevent the heat deterioration of substrate, preferably cooled down from substrate side.
In addition, as above-mentioned pulsed light, can use 1pm~1m wave-length coverage electromagnetic wave it is preferable to use
The electromagnetic wave (from far ultraviolet to far infrared) of the wave-length coverage of 10nm~1000 μm, further preferably using 100nm~2000nm
Wave-length coverage electromagnetic wave.As the example of such electromagnetic wave, gamma-rays, X ray, ultraviolet, visible ray, red can be enumerated
Outside line, microwave, electric wave of long wavelength side etc. compared with microwave.In addition, in the case where considering the conversion to heat energy, in wavelength too
In the case of short, the damage of resin substrate to carrying out pattern printing etc. is big, so as to not preferred.In addition, in the long feelings of wavelength
Under condition, it is impossible to efficiently absorb and generate heat, therefore it is not preferred.Therefore, the scope as wavelength, among above-mentioned wavelength,
The wavelength of the scope of scope particularly preferably from ultraviolet to infrared, more preferably 100~2000nm.
The irradiation time (on) of 1 time of pulsed light also depends on luminous intensity, but the preferably scope of 20 microsecond~50 millisecond.
If shorter than 20 microseconds, the sintering of metal nanometer line or metal nano-tube is difficult to, the effect of the performance raising of transparency electrode
Fruit step-down.In addition, if longer than 50 milliseconds, then sometimes because light deterioration, heat deterioration and base material is made a very bad impression, in addition, golden
Category nano wire or metal nano-tube easily blow winged.More preferably 40 microsecond~10 millisecond.For the above reasons, in present embodiment
In without using continuous light but use pulsed light.The irradiation of pulsed light is implemented also to have effect even if with single-shot, but can also
Implement repeatedly as described above.In the case of implementing repeatedly, (off) is spaced for irradiation, it is contemplated that productivity ratio, preferably 20 is micro-
Second~5 seconds, the scope of more preferably 2 milliseconds~2 seconds., can be close to continuous light, due to once if shorter than 20 microseconds
After irradiation, do not irradiated during letting cool, therefore have the possibility that base material is heated, temperature increases and deteriorated.In addition, such as
Fruit is longer than 5 seconds, then the process time is elongated, therefore not preferred.
In the case of the transparency electrode of manufacture present embodiment, on appropriate substrate, the saturating of present embodiment is used
The pattern of bright electric conductivity ink printing arbitrary shape, heated as needed after drying it, to the pattern, use xenon
Pulsed exposure lamp of gas formula etc., irradiation pulsewidth (on) are 20 microsecond~50 millisecond, the arteries and veins of more preferably 40 microsecond~10 millisecond
Wash off and engage the mutual intersection point of metal nanometer line or metal nano-tube.Here, engagement refers in metal nanometer line or metal
On the mutual intersection point of nanotube, the material (metal) of nano wire or nanotube absorbs pulsed light, more efficiently draws in cross section
Inner heat is played, thus the part is soldered.By the engagement, the company between the nano wire or nanotube of cross section can be made
Junction product increases and reduces sheet resistance.So, by irradiating pulsed light and the friendship of jointing metal nano wire or metal nano-tube
Point, forms metal nanometer line or metal nano-tube is changed into netted conductive layer.Therefore, it is possible to improve the electric conductivity of transparency electrode,
Its sheet resistance value is changed into 0.1~500 Ω/.In addition, the net that metal nanometer line or metal nano-tube are formed is not preferably not empty
Open the intensive state in compartment of terrain.Because if not spaced apart light decrease in transmission.
The transparency electrode obtained as described above is made up of single conductive layer, metal nanometer line and/or gold in the conductive layer
Belong to nanotube substantially uniform state in adhesive resin, and metal nanometer line and/or metal nano-tube have friendship each other
Fork point.The value of sheet resistance is 0.1~500 Ω/, and the scope of full light transmittance preferably 60~92%, haze value are excellent
Select 0.5~80% scope.
In addition, the surface roughness of obtained transparency electrode has an impact to the performance of organic EL element etc., it is desirable to height
Smoothly, specifically, for arithmetic average roughness Ra, Ra≤5nm, preferably Ra≤4nm, more preferably Ra≤1nm.Separately
Outside, r.m.s. roughness Rq is preferably 1nm~20nm scope, more preferably below 5nm.
Surface roughness Ra and r.m.s. roughness Rq are determined by percussion mode AFM (atomic force microscopy).Use
Device be NanoScopeIIIa Dimension 3000 (Digital Instruments societies system), as cantilever (probe),
Use NCH (monocrystalline silicon probe, Na ノ ワ ー Le De system).Membrane sample is attached at workbench after 1cm square is cut into, with adhesive tape
On.It is measured with the condition of 10 μm of square of scan size, scanning/line number 512 × 512, sweep speed 1.00s/ lines.Determine number
Smoothing correction is carried out according to use device accompanying software (Version 5.30r3.sr3), calculates Ra and Rq.
Transparent using the transparent conductivity ink print containing metal nanometer line and/or metal nano-tube and adhesive resin
In the case of electrode pattern, adhesive resin, which turns into, relaxes composition, and the surface roughness of transparent electrode pattern reduces, but is formed viscous
The planar film of mixture resin-coated metal nano wire and/or metal nano-tube, so the sheet resistance of transparent electrode pattern is very
Height, form the film of insulating properties.If surface roughness is not damaged to transparent electrode pattern irradiating pulsed light in this condition
And engage metal nanometer line and/or the mutual crosspoint of metal nano-tube, and remove the adhesive resin on surface and expose
A part for metal nanometer line and/or metal nano pipe surface, thus, it is possible to reduce sheet resistance.The condition of light irradiation also takes
Certainly in the material and thickness of the base material used, but for example use NovaCentrix societies system in light irradiation device
In the case of PulseForge3300, preferably in 200~5000mJ/cm of light exposure2, in the range of the μ s of time for exposure 20~200
Carry out light irradiation.
Embodiment
Hereinafter, embodiments of the invention are illustrated.In addition, following embodiment is for making the understanding of the present invention easy
Embodiment, the present invention do not limited by these embodiments.
＜ FeCl3The making ＞ of ethylene glycol solution (600 μ mol/Ls solution)
FeCl is weighed using 100ml measuring bottle3(Wako Pure Chemical Industries, Ltd.'s system, iron chloride (III)) 0.9732g
(0.006mol), ethylene glycol is added to 9 one-tenth of graticule or so, after being completely dissolved it, spent glycol is diluted to graticule.Measuring makes
The solution 1ml being in control with liquid relief, is added into 100ml measuring bottles, and spent glycol is diluted to graticule.
The making ＞ of ＜ nano silver wires
Respectively measured in reaction flask (capacity 150ml, external diameter 60mm) and beaker (capacity 100ml) 25g ethylene glycol (and
Wako Pure Chemical Industries Co. Ltd. system, ethylene glycol).Weigh PVP K-90 (Wako Pure Chemical Industries, Ltd.'s system)
0.2g(1.8mmol)、AgNO3(Wako Pure Chemical Industries, Ltd.'s system, silver nitrate) 0.25g (1.5mmol), by it respectively to anti-
Answer and be slowly added into flask and beaker while being stirred.After being completely dissolved, the solution in beaker is moved into reaction flask
In, then add the FeCl prepared3Ethylene glycol solution (600 μ mol/Ls solution) 3.413g (0.0018mmol), uses magnetic
Power agitator stirs solution 5 minutes.Afterwards, reaction flask is loaded to the organic synthesis plant of temperature stabilization at 150 DEG C
(EYELA Tokyo Physico-chemical Apparatus Co., Ltd. system, ケ ミ ス テ ー シ ョ Application PPV-CTRL1) heating response 1.5 hours.It is anti-in heating
Without stirring in answering.
Reaction solution before heating starts is water white transparency, but 5 minutes or so after reaction starts are changed into yellow, Zhi Houhuang
Discoloration is dense, is grey starting muddiness after about 30 minutes.It is overall to turn into light grey state after about 1 hour.
＜ post-processes ＞
After 1.5 hours, stop the heating of reaction flask, reaction solution is cooled to warm degree.In reaction vessel
The acetone of about 4 times of volumes of reaction solution is added, is stood after stirring, line is deposited in the bottom of reaction flask.
Using 3.0 μm of aperture, Fiber Diameter 47mm TFE PTFE film formula filter, sediment is being grasped
Pay attention to making filter moist while being filtered during work, enter the trapping of line sediment, afterwards, entered with ethanol
The cleaning of row PVP.After filtrate turns into transparent, filter is taken out, is impregnated in and washes out what is trapped in ethanol
Line.Afterwards, using vibration mechanism into dispersed wired alcohol dispersion liquid.Nano silver wire concentration is a part of uniform by taking
Dispersion liquid simultaneously passes through ICP luminescent spectrums (ICP-AES (Hitachi's Ha イ テ Network サ イ エ Application ス ICP emission spectroanalysis devices
Vista-pro)) analyze to determine.As a result, concentration is 0.2 mass %.
Fig. 2 (a), (b) represent the SEM pictures of the nano silver wire obtained.The SEM used is Hitachi's Ha イ テ Network Co. Ltd. systems
FE-SEM S-5200。
From Fig. 2 (a), (b), nano silver wire is wire, and the diameter of the line of the wire is about 70nm, and length is 10~20
μm, the line for growing into wire accounts for overall about more than 95%.It is in addition, remaining to be granular.
In addition, the length and diameter of nano silver wire are determined by SEM and TEM.It should be noted that the TEM used is
Jeol Ltd. TEM；JEOL, JEM-2100 transmission electron microscope.
The making ＞ of ＜ transparent conductivities ink
Embodiment 1
When preparing transparent conductivity ink, using commercially available nano silver wire dispersion liquid SLV-NW-35, (bluenano societies system is different
Propanol dispersion liquor, concentration 10mg/mL, the footpath 35nm of nano silver wire, about 15 μm of length (Directory Value)) it is used as raw material.Relative to this
In dipropylene glycol monomethyl ether (being bought by the Northeast chemical (strain) with reagent), 4.8g is at room temperature for nano silver wire dispersion liquid 25mL additions
PVP ((strain) Japanese catalyst system) 0.75g solution is dissolved with advance, after mixing, evaporates isopropanol, is carried out
Solvent is replaced.Afterwards, 19.2g テ Le ソ Le Block MTPH (Japanese テ Le ペ Application chemical (strain) system, isobornyl hexamethylene is added
Alcohol), (strain) シ ン キ ー society rotation-revolution vacuum mixer あ わ と り Practice Taros ARV-310 are used with rotating speed 1200rpm
Stirring 3 minutes, the concentration for obtaining nano silver wire is 1 mass %, the concentration of PVP is that 3 the transparent of mass % are led
Electrically ink.
Embodiment 2~6,8
Dipropylene glycol monomethyl ether solution that change is added relative to 25mL SLV-NW-35, PVP
Concentration and テ Le ソ Le Block MTPH amount, in addition, prepared respectively with operation similarly to Example 1.
Embodiment 7
Alcohol dispersion liquid using the nano silver wire obtained by above-mentioned synthesis is used as raw material.Dispersion solvent is ethanol, dense
Spend for 0.2 mass %, in addition, led by the way that the operation preparation same with the situation of the embodiment 1 using SLV-NW-35 is transparent
Electrically ink.
Comparative example 1
Ink without adhesive resin is also made by same operation.
For each ink, the viscosity at 25 DEG C is determined using Block Le ッ Network Off ィ ー ルド society type DV-II+Pro.Need to illustrate
, the rotor numbering used is 52.
Using these transparent conductivities ink, made using screen process press MT-320TVZ (マ イ Network ロ テ ッ Network (strain) system)
To print the test film (metal nanometer line layer) of 2.5cm square on the Le ミ ラ ー 125U98 (eastern beautiful (strain) system) of substrate.Afterwards,
With described in table 1 condition implement drying process, and using NovaCentrix societies PulseForge3300 irradiate 1 600V,
50 μ seconds (light exposure 953mJ/cm2) pulsed light.
Use Mitsubishi chemical Co., Ltd LORESTA-GP MCP-T6104 sonde methods surface resistivity, specific insulation
Determine device and sheet resistance value is determined to the transparency electrode after drying process (before light irradiation) and after light irradiation.In addition, use day
This electricity Se Industrial Co., Ltd nephelometer NDH2000 determines full light transmittance.
Table 1 show the viscosity, the nano silver wire concentration (calculated value) of electrode, thickness, light of ink burn till after sheet resistance,
Full light transmittance, surface roughness.
[table 1]
The OL on the column of the sheet resistance of pre-irradiation refers to exceed upper limit of detection.
In addition, in embodiment 3, solvent uses butyl acetate, because viscosity is too low, so passing through without using silk-screen printing
Bar coater makes film.In addition, in comparative example 1, film is made also by bar coater.
The thickness of the nesa coating of acquisition determines as follows.Sample formed with nesa coating is cut into suitably with cutting knife
Size after, for strengthened and with sample from SUS plates stretch out 1mm state with SUS thin plates clamp, be installed on SEM's
In sample mount, SEM cross-section is carried out.In addition, in embodiment 8 and comparative example 1, due to the resin component around filamentary silver
Few, so the sample of the film thickness measuring of the above method can not be manufactured subtly, thickness is not measured.
Understand, compared with the comparative example without adhesive resin, use the present invention of the adhesive resin containing ormal weight
Transparency electrode formed with transparent conductivity ink obtain embodiment nesa coating (transparency electrode) in, obtain small surface
Roughness.
Claims (10)
1. a kind of transparency electrode, it is characterised in that containing metal nanometer line and/or metal nano-tube and in 5~40 DEG C of scope
Thermosetting or thermoplastic binder resins without mobility, relative to the metal nanometer line and/or metal nano-tube 100
Mass parts, containing 300~2500 mass parts described adhesive resins, the sheet resistance of the electrode is 0.1~500 Ω/, institute
Surface arithmetic average roughness Ra≤5nm of electrode is stated, the electrode is made up of single conductive layer.
2. transparency electrode according to claim 1, the surface arithmetic average roughness Ra≤4nm.
3. transparency electrode according to claim 1 or 2, metal nanometer line and/or metal nano-tube in the transparency electrode
Content be 4~50 mass %.
4. transparency electrode according to claim 1 or 2, the metal of the metal nanometer line and/or metal nano-tube contains
Silver.
5. transparency electrode according to claim 3, the metal of the metal nanometer line and/or metal nano-tube contains silver.
6. according to the transparency electrode any one of claim 1,2 and 5, described adhesive resin is selected from poly N-vinyl
At least one of pyrrolidones, poly-N-vinylcaprolactam, poly N-ethylene yl acetamide, polyvinylformamide.
7. transparency electrode according to claim 3, described adhesive resin is selected from poly N-vinyl pyrrolidone, poly- N-
At least one of caprolactam, poly N-ethylene yl acetamide, polyvinylformamide.
8. transparency electrode according to claim 4, described adhesive resin is selected from poly N-vinyl pyrrolidone, poly- N-
At least one of caprolactam, poly N-ethylene yl acetamide, polyvinylformamide.
9. the manufacture method of transparency electrode according to any one of claims 1 to 8, it is characterised in that there is following process：
Print the electrode pattern of desired shape by intaglio printing or silk-screen printing on substrate using transparent conductivity ink
Process, the transparent conductivity ink obtains as follows：The scope made at 5~40 DEG C does not have the thermosetting or heat of mobility
Plastic binder resin is dissolved in solvent and obtains solution, metal nanometer line and/or metal nano-tube is scattered in the solution,
In the transparent conductivity ink, relative to the metal nanometer line and/or the mass parts of metal nano-tube 100, containing 300~
The described adhesive resin of 2500 mass parts；And
To the process of the electrode pattern irradiating pulsed light of printing.
10. a kind of transparency electrode formation transparent conductivity ink for being used to form the transparency electrode described in claim 1, its feature
It is,
Containing metal nanometer line and/or metal nano-tube, solvent and be dissolved in solvent in 5~40 DEG C of scope without flowing
The thermosetting of property or thermoplastic binder resins, relative to the metal nanometer line and/or the mass parts of metal nano-tube 100, contain
There are 300~2500 mass parts described adhesive resins, viscosity of the transparent conductivity ink at 25 DEG C is 300~2 ×
105mPa·s。
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| JP2013172238 | 2013-08-22 | ||
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| PCT/JP2014/071427 WO2015025792A1 (en) | 2013-08-22 | 2014-08-14 | Transparent electrode and method for producing same |
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| US (1) | US9854670B2 (en) |
| JP (2) | JP6563811B2 (en) |
| KR (1) | KR101812531B1 (en) |
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| CN103068573A (en) * | 2011-03-10 | 2013-04-24 | 松下电器产业株式会社 | Transparent conductive film, substrate with transparent conductive film, and organic electroluminescence element using same |
| JP2012216535A (en) * | 2011-03-31 | 2012-11-08 | Mitsubishi Chemicals Corp | Transparent conductive film containing metal nanowire and coating liquid thereof |
| CN103106950A (en) * | 2013-01-10 | 2013-05-15 | 中国航空工业集团公司北京航空材料研究院 | Conductive foam and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2020013792A (en) | 2020-01-23 |
| TW201522049A (en) | 2015-06-16 |
| US9854670B2 (en) | 2017-12-26 |
| JP6563811B2 (en) | 2019-08-21 |
| WO2015025792A1 (en) | 2015-02-26 |
| JP6807995B2 (en) | 2021-01-06 |
| KR101812531B1 (en) | 2017-12-27 |
| JPWO2015025792A1 (en) | 2017-03-02 |
| KR20160014703A (en) | 2016-02-11 |
| TWI655090B (en) | 2019-04-01 |
| CN105493203A (en) | 2016-04-13 |
| US20160205775A1 (en) | 2016-07-14 |
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